Random and block copolymers based on 4-methyl-1-pentene and 1-pentene

C.D. Descour, A.M.J.T. Meijer-Vissers, T. Macko, M. Parkinson, D. Cavallo, M. Drongelen, van, G. Hubner, J.G.P. Goossens, R. Duchateau

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

The zirconium acetamidinate catalyst {Cp*Zr(Me)2[N(Et)C(Me)N(tBu)]} (Cp* = ¿5-C5Me5) was used to synthesize both random and block copolymers based on 4-methyl-1-pentene (4M1P) and 1-pentene. The polymers have been characterized by NMR spectroscopy, SEC, DSC, high temperature HPLC and CRYSTAF. Unexpectedly, the yields and molecular weights decreased with increasing amounts of 1-pentene. The reason for this behavior is that 1-pentene occasionally undergoes 2,1-misinsertions trapping the catalyst in a dormant state. These 2,1-misinsertions do not seem to occur with the bulky 4M1P (branched a-olefin). Adding a small amount of ethylene reactivates the catalyst. Unlike most semi-crystalline polymers, the density of the crystalline phase of isotactic P4M1P can be lower than of the amorphous phase, when crystallized under very high pressures. To characterize this peculiar behavior of 4M1P-based polymers, various samples have been subjected to Pressure-Volume-Temperature (PVT) measurements. While the P4M1P homopolymers and block copolymers show the expected decrease in specific volume upon crystallization, the 4M1P-rich random copolymers proved not to vary in specific volume under the same conditions
Original languageEnglish
Pages (from-to)3096-3106
JournalPolymer
Volume53
Issue number15
DOIs
Publication statusPublished - 2012

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Block copolymers
Density (specific gravity)
Catalysts
Polymers
Crystalline materials
Volume measurement
Homopolymerization
Zirconium
Temperature measurement
Nuclear magnetic resonance spectroscopy
Olefins
Ethylene
Copolymers
Crystallization
Molecular weight
Alkenes
1-pentene
Temperature

Cite this

Descour, C. D., Meijer-Vissers, A. M. J. T., Macko, T., Parkinson, M., Cavallo, D., Drongelen, van, M., ... Duchateau, R. (2012). Random and block copolymers based on 4-methyl-1-pentene and 1-pentene. Polymer, 53(15), 3096-3106. https://doi.org/10.1016/j.polymer.2012.05.030
Descour, C.D. ; Meijer-Vissers, A.M.J.T. ; Macko, T. ; Parkinson, M. ; Cavallo, D. ; Drongelen, van, M. ; Hubner, G. ; Goossens, J.G.P. ; Duchateau, R. / Random and block copolymers based on 4-methyl-1-pentene and 1-pentene. In: Polymer. 2012 ; Vol. 53, No. 15. pp. 3096-3106.
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abstract = "The zirconium acetamidinate catalyst {Cp*Zr(Me)2[N(Et)C(Me)N(tBu)]} (Cp* = ¿5-C5Me5) was used to synthesize both random and block copolymers based on 4-methyl-1-pentene (4M1P) and 1-pentene. The polymers have been characterized by NMR spectroscopy, SEC, DSC, high temperature HPLC and CRYSTAF. Unexpectedly, the yields and molecular weights decreased with increasing amounts of 1-pentene. The reason for this behavior is that 1-pentene occasionally undergoes 2,1-misinsertions trapping the catalyst in a dormant state. These 2,1-misinsertions do not seem to occur with the bulky 4M1P (branched a-olefin). Adding a small amount of ethylene reactivates the catalyst. Unlike most semi-crystalline polymers, the density of the crystalline phase of isotactic P4M1P can be lower than of the amorphous phase, when crystallized under very high pressures. To characterize this peculiar behavior of 4M1P-based polymers, various samples have been subjected to Pressure-Volume-Temperature (PVT) measurements. While the P4M1P homopolymers and block copolymers show the expected decrease in specific volume upon crystallization, the 4M1P-rich random copolymers proved not to vary in specific volume under the same conditions",
author = "C.D. Descour and A.M.J.T. Meijer-Vissers and T. Macko and M. Parkinson and D. Cavallo and {Drongelen, van}, M. and G. Hubner and J.G.P. Goossens and R. Duchateau",
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Descour, CD, Meijer-Vissers, AMJT, Macko, T, Parkinson, M, Cavallo, D, Drongelen, van, M, Hubner, G, Goossens, JGP & Duchateau, R 2012, 'Random and block copolymers based on 4-methyl-1-pentene and 1-pentene', Polymer, vol. 53, no. 15, pp. 3096-3106. https://doi.org/10.1016/j.polymer.2012.05.030

Random and block copolymers based on 4-methyl-1-pentene and 1-pentene. / Descour, C.D.; Meijer-Vissers, A.M.J.T.; Macko, T.; Parkinson, M.; Cavallo, D.; Drongelen, van, M.; Hubner, G.; Goossens, J.G.P.; Duchateau, R.

In: Polymer, Vol. 53, No. 15, 2012, p. 3096-3106.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Random and block copolymers based on 4-methyl-1-pentene and 1-pentene

AU - Descour, C.D.

AU - Meijer-Vissers, A.M.J.T.

AU - Macko, T.

AU - Parkinson, M.

AU - Cavallo, D.

AU - Drongelen, van, M.

AU - Hubner, G.

AU - Goossens, J.G.P.

AU - Duchateau, R.

PY - 2012

Y1 - 2012

N2 - The zirconium acetamidinate catalyst {Cp*Zr(Me)2[N(Et)C(Me)N(tBu)]} (Cp* = ¿5-C5Me5) was used to synthesize both random and block copolymers based on 4-methyl-1-pentene (4M1P) and 1-pentene. The polymers have been characterized by NMR spectroscopy, SEC, DSC, high temperature HPLC and CRYSTAF. Unexpectedly, the yields and molecular weights decreased with increasing amounts of 1-pentene. The reason for this behavior is that 1-pentene occasionally undergoes 2,1-misinsertions trapping the catalyst in a dormant state. These 2,1-misinsertions do not seem to occur with the bulky 4M1P (branched a-olefin). Adding a small amount of ethylene reactivates the catalyst. Unlike most semi-crystalline polymers, the density of the crystalline phase of isotactic P4M1P can be lower than of the amorphous phase, when crystallized under very high pressures. To characterize this peculiar behavior of 4M1P-based polymers, various samples have been subjected to Pressure-Volume-Temperature (PVT) measurements. While the P4M1P homopolymers and block copolymers show the expected decrease in specific volume upon crystallization, the 4M1P-rich random copolymers proved not to vary in specific volume under the same conditions

AB - The zirconium acetamidinate catalyst {Cp*Zr(Me)2[N(Et)C(Me)N(tBu)]} (Cp* = ¿5-C5Me5) was used to synthesize both random and block copolymers based on 4-methyl-1-pentene (4M1P) and 1-pentene. The polymers have been characterized by NMR spectroscopy, SEC, DSC, high temperature HPLC and CRYSTAF. Unexpectedly, the yields and molecular weights decreased with increasing amounts of 1-pentene. The reason for this behavior is that 1-pentene occasionally undergoes 2,1-misinsertions trapping the catalyst in a dormant state. These 2,1-misinsertions do not seem to occur with the bulky 4M1P (branched a-olefin). Adding a small amount of ethylene reactivates the catalyst. Unlike most semi-crystalline polymers, the density of the crystalline phase of isotactic P4M1P can be lower than of the amorphous phase, when crystallized under very high pressures. To characterize this peculiar behavior of 4M1P-based polymers, various samples have been subjected to Pressure-Volume-Temperature (PVT) measurements. While the P4M1P homopolymers and block copolymers show the expected decrease in specific volume upon crystallization, the 4M1P-rich random copolymers proved not to vary in specific volume under the same conditions

U2 - 10.1016/j.polymer.2012.05.030

DO - 10.1016/j.polymer.2012.05.030

M3 - Article

VL - 53

SP - 3096

EP - 3106

JO - Polymer

JF - Polymer

SN - 0032-3861

IS - 15

ER -

Descour CD, Meijer-Vissers AMJT, Macko T, Parkinson M, Cavallo D, Drongelen, van M et al. Random and block copolymers based on 4-methyl-1-pentene and 1-pentene. Polymer. 2012;53(15):3096-3106. https://doi.org/10.1016/j.polymer.2012.05.030